EP0932372B1 - Uv-cured resin coated dental floss - Google Patents

Uv-cured resin coated dental floss Download PDF

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Publication number
EP0932372B1
EP0932372B1 EP97930144A EP97930144A EP0932372B1 EP 0932372 B1 EP0932372 B1 EP 0932372B1 EP 97930144 A EP97930144 A EP 97930144A EP 97930144 A EP97930144 A EP 97930144A EP 0932372 B1 EP0932372 B1 EP 0932372B1
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EP
European Patent Office
Prior art keywords
dental floss
floss
compound
resin
filament
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP97930144A
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German (de)
English (en)
French (fr)
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EP0932372A1 (en
Inventor
David L. Anglin
Casper W. Chiang
Larry H. Luebbert
Michael F. Roberts
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Gillette Canada Inc
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Gillette Canada Inc
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C15/00—Devices for cleaning between the teeth
    • A61C15/04—Dental floss; Floss holders
    • A61C15/041—Dental floss
    • A61C15/042—Dental floss comprising protuberances along its length, e.g. balls or knots
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters

Definitions

  • Tooth decay and dental disease can be caused by bacterial action resulting from the formation of plaque about the teeth and/or the entrapment of food particles in interstices between the teeth. Removal of plaque and entrapped food particles reduces the incidence of caries, gingivitis, and mouth odors as well as generally improving oral hygiene.
  • Conventional brushing has been found to be inadequate for removing all entrapped food particles and plaque.
  • dental flosses and tapes have been recommended.
  • Dental flosses including a thickened "brush” portion have been developed. These flosses may also include a thin “floss” portion and a threader. The brush portion, when drawn between tooth surfaces, provides good cleaning action which removes materials left by a standard thin floss used alone.
  • Dental flosses both in brush and thin floss form, often include additives such as flavors or colors. These flavors have been conventionally applied by coating the additive onto the surface of the floss.
  • polymers coating a filament are applied as solutions dissolved in a solvent.
  • the production of polymer-covered filaments entails delay in the time required for the solvent to evaporate, generation of polluting solvent vapors, and the danger of residual unevaporated solvents.
  • the present invention features a dental floss having improved abrasivity consisting of a dental filament coated with a UV-curable resin. Improved abrasivity is achieved by coating the fibers with a resin binder curable by exposure to ultraviolet (UV) radiation.
  • the resin is a composition comprising a clear oligomer resin and a UV-sensitive component.
  • the oligomer resin is comprised of monomers having one or more cross-linkable functional groups such as acrylate or methacrylate.
  • the monomers are epoxy acrylates, polyurethane acrylates, polyester acrylates, and acrylic acrylates.
  • the UV-sensitive component is a photoinitiating compound which absorbs ultraviolet light and initiates polymerization of the monomers.
  • the photoinitiating compound is benzoin, a benzoin alkyl ether, a benzyl ketal, an acetophenone derivative, a benzophenone, Michler's ketone, an ⁇ -acyloxime ester, a thioxanthone or a thioxanthone derivative, a quinone, anthraquinone or derivative, an organic peroxide, an organic sulfur compound, a metal compound or metal ion, an alkali dichromate, an organic phosphorus compound, a chlorosilane or an azo compound.
  • the photoinitiator is benzophenone.
  • the UV-cured resin coated dental floss of the invention may further comprise additional components that provide desired floss properties and/or health treatment.
  • the UV-cured resin includes a compound for control of the floss friction coefficent, e.g., abrasivity.
  • polytetrafluoroethylene (PTFE or Teflon®) powder is added to the UV resin formulation.
  • PTFE or Teflon® polytetrafluoroethylene
  • a compound is added to the UV-cured resin formulation for anti-caries tooth treatment.
  • the anti-caries treatment compound is sodium fluoride, stannous fluoride, or monosodium fluoride phosphate.
  • the UV-curable resin coated dental floss of the invention may have one or more distinct sections, including 1) a conventional floss section for cleaning the interproximal surfaces between the teeth, 2) a bulked brush section having improved abrasivity toward plaque and a larger dimension than the floss.
  • the coated dental filaments of the invention may be composed of monofilaments, e.g., filaments composed of one fiber, and multifilaments, e.g., strands having multiple fibers.
  • Specific embodiments of the method of the invention include coating bulked or non-bulked filaments having a high or low elasticity, respectively, to produce dental floss having improved abrasivity.
  • the invention further features a method for producing a dental floss having improved abrasivity.
  • An oligomer resin containing a photoinitiating system is coated onto a dental fiber and exposed to UV radiation such that the resin coat is cured to the desirable degree of hardness.
  • the method of the invention allows the degree of abrasivity of a floss to be controlled as desired.
  • One object of the invention is to provide a dental floss having improved abrasivity.
  • Another object of the invention is to provide an improved method of producing a coated dental floss having improved abrasivity.
  • One advantage of the invention is the production of a resin-coated dental floss without the use of solvents.
  • Fig. 1 is a schematic representation of a dental floss having distinct floss, brush, and threader portions.
  • Fig. 2 illustrates a method of coating a yarn with the UV-cured resins of the invention.
  • Yarn (1) is coated at a station consisting of a yarn unwind station (2), a tensioning device (3), a coating die (4), a medium pressure mercury arc lamp (5), and a speed controlled winding station (6).
  • a dental floss is meant a filament or yarn suitable for use for removal of food particles in the interstices between teeth.
  • a dental floss may be composed of a single filament (monofilament) yarn of a multifilament yarn, and may contain discrete sections of different thickness, e.g., a threader portion and a brush portion (Fig. 1).
  • UV cured resin By the term “UV cured resin” , “ultraviolet-curable resin” , or “UV-cured resin” , and the like, is meant a coating which achieves the desired degree of hardness upon exposure to ultraviolet radiation. This occurs due to the presence of a photoinitiating compound which absorbs UV light, generates a free radical, and causes cross-linking of functional groups on resin monomers.
  • cross-linkable functional group is meant a chemical group, e.g., an acrylate or methacrylate, which is induced to react with another functional group upon activation by a free radical, resulting in cross-linking of the monomers containing the functional groups.
  • photoinitiator system a molecule which absorbs visible or ultraviolet light, forming an excited state which can then either fragment into free radical functional groups ("type I") capable of initiating polymerization of the monomers, or alter a second molecule by abstracting a hydrogen from the second molecule and converting the second molecule into a free radical capable of initiating polymerization ("type II" photoinitiator).
  • type I free radical functional groups
  • type II free radical capable of initiating polymerization
  • the term “bulked” yarn is meant a multifilament strand composed of multiple individual filaments, where the individual filaments are in a random nonlinear conformation and remain entangled together. This results in an overall shortening of the overall length of a section of yarn relative to the length of the yarn when the filaments are placed under tension.
  • the coating of solid material onto a dental material is generally achieved by dissolving the coating material in a solvent such as ethanol, acetone, ethyl acetate, triethylene glycol.
  • a solvent such as ethanol, acetone, ethyl acetate, triethylene glycol.
  • Commonly used natural and synthetic resins are generally dissolved in a solvent, and the resin becomes hard after evaporation of the solvent. Examples of commonly used resins are shellac, benzoin resin, polyvinyl pyrrolidone, and colophony.
  • U.S. Patent No. 5,393,516 describes the coating of dental material with an antibacterial chlorhexidine adduct. The chlorhexidine adduct is formulated into a light-curing sealant applied with a paintbrush onto a molar fissure.
  • Dental filaments for use in the flosses of the invention are preferably monofilaments or multifilaments.
  • the dental floss is manufactured as multicomponent coextruded filaments.
  • multicomponent is meant a filament having two or more components; by “coextruded” is meant that at least two of the components are present in the form of substantially separate phases having a distinct interface between them, rather than being intermixed.
  • the filaments may be formed by processes referred to in the art as “coextruded”, but may also encompass filaments having the structure described above which are manufactured by other processes known to the art
  • the dental flosses having improved abrasivity include bulked and non-bulked fibers.
  • a bulked nylon yarn alone is not adequate in stiffness to form an abrasive brush. If stretched or immersed in water its brush geometry will collapse.
  • a bulked yarn needs to have its geometry stabilized with a polymer over-coating. This coating acts to bind individual filaments of the bulked yarn together at contact points. The result of binding of filament to filament is a network structure similar to a fishing net but with three dimensions, which is flexible yet maintains its overall geometry when stretched or immersed.
  • the abrasivity of such a bulked brush section is dependent on the properties of the polymer over-coating. If a brush section has a soft stretchy over-coating, the brush will be soft and stretchy; a hard brittle over-coating results in a brush with a hard brittle feel.
  • the properties of a dental floss when wet are important. If the bulked nylon brush polymer over-coating is water soluble, the brush structure is likely to collapse when wet. A highly hydrophilic coating will be overly softened when wet, resulting in decreased abrasivity of the floss and less effectiveness for plaque removal.
  • the resin is composed of a mixture of crosslinkable resin or resins and a UV-sensitive component which initiates polymerization upon exposure to UV radiation.
  • the resin is a clear copolymer resin of a relatively high molecular weight, such as a polyurethane with molecular weight 1000.
  • a variety of resinous compositions are known in the art to be susceptible to crosslinking by means of exposure to free radicals derived from excitation of added photoinitiators by (UV) radiation.
  • Certain acrylate, methacrylate, and bismaleate vinyl ether blends are susceptible; see, for example, U.S. Patent Nos. 3,066,112; 3,179,623; 3,256,266 and 3,301,743.
  • Resinous composition such as urethane acrylates can be combined with radiation sensitive initiators such as benzophenone, and are cured upon exposure to UV radiation. In thin films, the cure can be accomplished in less than 1 second.
  • Methods of photocuring a UV-sensitive resin are known in the art. See, for example, U.S. Patent No. 4,380,435.
  • UV-curable resins have molecular weights from 150 to 550. Generally, larger molecules pose a decreased toxicity risk than smaller molecules.
  • UV-curable monomer trimethylolpropane triacrylate (TMPTA) has a molecular weight of 296 and a toxicity (Drais) value of 5. When the molecular weight of TMPTA is increased to 912 by ethoxylation, the toxicity value drops to 0.
  • the preferred oligomer monomer used in the present invention such as polyurethane, has a high molecular weight, e.g., 1000.
  • the UV-curable resin of the present invention is composed of a monofunctional or multifunctional monomer molecule and a photoinitiating compound.
  • Monomers typically used for UV curing have an acrylate or methacrylate functional groups.
  • the number of acrylate, methacrylate, bismaleates and vinyl ether groups per monomer molecule is typically two, e.g., diacrylates or dimethacrylates, but monomers may be monofunctional or multifunctional.
  • Photoinitiators and photosensitizers absorb ultraviolet light to form free radical groups which can initiate polymerization.
  • a critical element in the selection of the appropriate photoinitiating compound is that it absorb light at a wavelength at which the remaining resin components do not absorb.
  • the appropriate photoinitiator must be soluble in the selected resin monomer. Additionally, the photoinitiator must have a high activity so that it initiates polymerization at very low concentrations, and must be nontoxic to humans in the final polymer.
  • Suitable photoinitiators include benzoins, benzoin alkyl ethers, benzyl ketals, acetophenone derivatives, benzophenones, Michler's ketone, ⁇ -acyloxime esters, thioxanthones or thioxanthone derivatives, quinones, anthraquinones or derivatives, organic peroxides, organic sulfur compounds, metal compounds or metal ions, alkali dichromates, organic phosphorus compounds, chlorosilanes and azo compounds.
  • Polymerization of the resin on the floss/filament material is accomplished by exposure of the UV-sensitive photoinitiator and free radical curable resin to UV radiation.
  • the source of UV radiation is a medium pressure mercury arc lamp.
  • resin-covered floss can be exposed to UV radiation from a commercial 85 watt Mercury vapor lamp for a time sufficient to cure the resin.
  • Other sources of UV radiation known in the art may be used in the method of the invention such that the resin exhibits a desired hardness value, as determined by methods known in the art, including Barcoll or Vickers hardness scores (Mark's standard Handbook for Mechanical Engineers, 9th Ed., pp. 5-13).
  • Degree of cure is determined by measuring the solubility of the cured UV polymer in an appropriate organic solvent. Uncured monomers are completely soluble in organic solvents and will extract out of a partially cured UV resin into an appropriate solvent. Extraction amount decreases as degree of cure increases. A fully cured, cross-linked polymer will be insoluble in solvents. Additives which do not crosslink with the UV resins such as type II photoinitiators or their reaction products will be extractable after the UV resin polymerizes.
  • the degree of cure of the UV-cured floss of the invention is determined by refluxing the floss in a suitable solvent. For example, in one method of determining degree of cure, refluxing floss that has been coated with a UV-curable coating in placed in 50:50 water/ethanol for 24 hours; the solvent is decanted and evaporated, and the residue weighed. The determination of the extractable portion of the coating provides a measure of the degree of cure.
  • This degree of cure extraction test can be used to optimize the UV exposure required to cure a UV coating for specific coating formulations.
  • a UV curable mixture can be coated onto the floss, passed through a 300 watt per inch medium pressure mercury arc UV lamp at a variety of speeds, and the percent extractable content after refluxing for 24 hours in a 50:50 water/ethanol solution determined.
  • UV-resin coated dental floss for use in the oral cavity of a human requires the careful selection of materials which will produce a floss with the desired mechanical and safety characteristics.
  • the present invention provides a series of test protocols and test results that must be achieved in order to achieve the UV-resin coated dental floss of the invention. Specifically, final UV-cured resins and photoinitiating compounds must be nontoxic to humans and nonsensitizing in the oral cavity.
  • one or more specific compounds can be added to the UV-curable resin coating for controlling the floss friction coefficient.
  • the compound added for controlling the floss friction coefficient is polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • a preferred floss friction coefficient is between 0.08 and 0.25.
  • PTFE has a coefficient of friction value of 0.04. The addition of PTFE to the UV resin composition results in a lowering of the coefficient of friction value of the floss.
  • Example 1 describes the test protocols used to evaluate the acceptability each component of the UV- curable resin composition in terms of toxicity (Example 1) and mechanical properties such as abrasiveness, brittleness, and flexibility (Example 2).
  • Example 3 describes the test protocols used to determine important processibility characteristics, for example, ease of handling (viscosity and sensitivity to UV light ( ⁇ )).
  • Example 4 evaluates three UV-cured resin formulations for the threader portion of a dental floss in terms of their mechanical and toxic properties.
  • Example 5 provides detailed toxicity results for a UV-cured resin formulated for application to the brush portion of a dental floss.
  • Example 6 evaluates a UV-cured coating formulation in terms of percent extractables and toxicity.
  • Cytotoxicity is evaluated by using the USP Elution Test Method (MG057), which measures the biological reactivity of polymeric materials. Briefly, monolayers of L-929 mouse fibroblast cells were grown to conf luency in duplicate flasks and exposed to an extract of the test article. The extract was prepared according to USP guidelines by placing the test article in 13 ml of MEM and extracting for 24 hours at 37°C. The current NAmSA positive control was used as a positive control and a USP negative bioreaction control was used as a negative control. The cells were examined for evidence of cytotoxic effect after exposure to the extracts for 48 hours at 37°C. Reactivity and grade were recorded according to Table 1. The NAmSA positive control was scored at 24 hours.
  • MG057 USP Elution Test Method
  • the test article meets the requirements of USP if the biological response is less than or equal to grade 2 (Mild).
  • GRADE REACTIVITY OBSERVATIONS 0 None Discrete intracytogranules; no cell lysis 1 Slight Not more than 20% of cells are round, loosely attached and without intracytoplasmic granules; some lysed cells are present. 2 Mild Not more than 50% of the cells are round and devoid of intracytoplasmic granules; extensive cell lysis and empty areas between cells. 3 Moderate Not more than 70% of the cell monolayer contain rounded and/or lysed cells. 4 Severe Nearly complete destruction of the cell monolayer.
  • Sensitization Test Sensitization was measured with the Repeated Insulin Patch Test (RIPT) (Belsity (1989) J. Am. Acad. Dermatol. 21:822-829). 40 grams of floss or threader were incubated at 37°C in 200 ml of 0.9% saline for 24 h. The saline was then sterilized by filtration through a 0.2 micron filter. In the "induction phase" of the test, approximately 0.2 ml of the test solution was applied as a patch to the back of the hand adjacent to the spinal midline of 50 male or female adult human volunteer subjects. The subjects were instructed to remove the patch 24 h after application. The procedure was repeated 3 times per week (Monday, Wednesday, Friday) for 3 weeks.
  • RIPT Repeated Insulin Patch Test
  • a challenge patch with the same amount of test extract previously applied was applied to a previously unpatched test site approximately 2 weeks after the induction phase was complete. The site was scored 24 and 72 h after application.
  • Flexibility and brittleness are measured using an Instron stress strain tester on cast films of polymer (ASTM D638).
  • Viscosity is determined with a rheometer having cone and plate geometry, constant stress mode (TA Associates).
  • Test results The resin provided adequate stiffness and a smooth surface. The resin passed the cytotoxicity test (0).
  • a resin having a softer finish is preferred for coating onto the brush portion of dental floss.
  • the following formula was evaluated by coating onto 640 denier nylon yarn at 15 feet per minute and UV curing with a 300 watt per inch medium pressure mercury vapor light: Brush Formula: Radcure Ebecryl 8402 93% Radcure Ebecryl BPO 7%
  • the Radcure 8402 formulation had a cytotoxicity score of "1" (Table 2).
  • a B Negative Control A Negative Control B Confluent Monolayer - - + + % Cells without Intracellular Granulation 10 10 0 0 % Rounding 10 10 0 0 % Lysis 10 10 0 0 Grade 1 1 0 0 Reactivity Slight Slight None None
  • Coating of floss with UV resins was accomplished on a coating line consisting of a yarn unwind station, a tensioning device, a coating die (Fig. 2), a medium pressure mercury arc lamp, and a speed controlled winding station.
  • the UV curable resin was supplied to the extrusion die through a side injection port where it is delivered to the yarn at a controlled rate.
  • the exit orifice of the extrusion die was sufficiently narrow to spread the UV resin uniformly on the yarn.
  • the coating composition Radcure 8402:220:BPO (46.5:46.5:5:7) was coated and cured as described above at a variety of speeds, and percent extractables determined. The following results were obtained with the use of a Fusion Systems Model F300 medium pressure mercury arc UV lamp.
  • the stiffness of this composition was compared with that of the conventional solvent-based polyurethane threader. As measured by Gurley stiffness, the conventional threader had a stiffness of 2.8 with a 38% coating (% of yarn substrate), while the UV formulation had a stiffness of 3.3 with a lower coating weight of 33%. Speed (ft/min) UV Exposure Time (sec) % Extractable Cytotoxicity 22.5 0.89 1.1 0 26 0.77 1.0 0 30 0.67 1.7 4
  • Radcure 8402 Sodium fluoride (2.2%, 4.4%, and 6.6%) was added to a 95:5 ratio of Radcure 8402 and BPO. After coating and UV curing onto nylon yarn as described in Example 3 above, the release of fluoride was measured. Fluoride release was determined by stirring a 10 meter length of floss in TISAB II water and measuring the fluoride concentration with an Orion 96-O9BN fluoride specific electrode. The results are shown in Table 4: Radcure 8402:BPO (% sodium fluoride) Sodium Fluoride Release (mg/0.5 m floss) 2.2 0.05 4.4 0.15 6.6 0.20 Commercial Floss 0.16
  • the method used to add sodium fluoride to commercially available dental floss was adding sodium fluoride to a wax, and coating the wax onto nylon yarn.
  • the addition of sodium fluoride to a commercial floss was found to weaken the wax coating, resulting in a dental floss more prone to fray between teeth.
  • the UV-cured floss containing sodium fluoride was not prone to fraying.
  • a UV-cured dental floss with flattened geometry was produced by first coating nylon yarn as with the composition of Example 3 above, and UV-curing the floss while it was in contact with the surface of a drum. This allowed the coated uncured floss to flatten against the drum surface and to be fixed in that geometry by exposure to UV light. A flattened floss was found to be easier to insert between teeth relative to floss having a round geometry.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dentistry (AREA)
  • Dental Preparations (AREA)
  • Paints Or Removers (AREA)
  • Cosmetics (AREA)
EP97930144A 1996-09-13 1997-06-19 Uv-cured resin coated dental floss Expired - Lifetime EP0932372B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US712513 1996-09-13
US08/712,513 US6293287B1 (en) 1996-09-13 1996-09-13 UV-cured resin-coated dental floss
PCT/US1997/010677 WO1998010710A1 (en) 1996-09-13 1997-06-19 Uv-cured resin coated dental floss

Publications (2)

Publication Number Publication Date
EP0932372A1 EP0932372A1 (en) 1999-08-04
EP0932372B1 true EP0932372B1 (en) 2003-03-26

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EP97930144A Expired - Lifetime EP0932372B1 (en) 1996-09-13 1997-06-19 Uv-cured resin coated dental floss

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US (1) US6293287B1 (pt)
EP (1) EP0932372B1 (pt)
JP (1) JP4294094B2 (pt)
KR (1) KR100469601B1 (pt)
CN (1) CN1147274C (pt)
AU (1) AU714546B2 (pt)
BR (1) BR9711773A (pt)
CA (1) CA2264883C (pt)
DE (1) DE69720232T2 (pt)
ES (1) ES2190536T3 (pt)
WO (1) WO1998010710A1 (pt)

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WO2009132474A1 (zh) * 2008-04-29 2009-11-05 Hsu Hanchung 沾黏粉末的牙线
US20100028527A1 (en) * 2008-07-31 2010-02-04 Harold Ochs Process for Coating Dental Tape
US20100024721A1 (en) * 2008-07-31 2010-02-04 Harold Ochs Apparatus for Coating Dental Tape
US8316865B2 (en) * 2008-07-31 2012-11-27 Mcneil-Ppc, Inc. Process for winding dental tape
US20100024722A1 (en) * 2008-07-31 2010-02-04 Harold Ochs Apparatus for Coating Dental Tape
RU2529401C2 (ru) * 2010-02-08 2014-09-27 Дзе Проктер Энд Гэмбл Компани Зубная нить с покрытием уменьшенной неравномерности
US8789542B2 (en) * 2010-12-31 2014-07-29 Julian Omidi Multi-edge dental floss
CN104970896B (zh) * 2015-07-10 2017-03-22 苏州登特商贸有限公司 牙线的制作方法及填补牙缝的方法
CN113062000B (zh) * 2021-03-15 2022-07-22 上海灵氟隆膜技术有限公司 一种聚四氟乙烯牙线制备方法及系统

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CA2264883A1 (en) 1998-03-19
AU714546B2 (en) 2000-01-06
BR9711773A (pt) 1999-08-24
CN1147274C (zh) 2004-04-28
CN1230101A (zh) 1999-09-29
ES2190536T3 (es) 2003-08-01
EP0932372A1 (en) 1999-08-04
KR20000036008A (ko) 2000-06-26
US6293287B1 (en) 2001-09-25
WO1998010710A1 (en) 1998-03-19
JP2001500405A (ja) 2001-01-16
AU3404697A (en) 1998-04-02
DE69720232T2 (de) 2003-12-04
JP4294094B2 (ja) 2009-07-08
CA2264883C (en) 2005-08-23
KR100469601B1 (ko) 2005-02-02
DE69720232D1 (de) 2003-04-30

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